CA2335481C - Organometallic compositions - Google Patents
Organometallic compositions Download PDFInfo
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- CA2335481C CA2335481C CA002335481A CA2335481A CA2335481C CA 2335481 C CA2335481 C CA 2335481C CA 002335481 A CA002335481 A CA 002335481A CA 2335481 A CA2335481 A CA 2335481A CA 2335481 C CA2335481 C CA 2335481C
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- polyisocyanate
- acetoacetate ester
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- acetoacetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
Abstract
An organometallic composition comprises a complex of at least one metal selected from the group consisting of titanium, zirconium and hafnium and an acetoacetate ester in which the molar ratio of Ti or Hf to acetoacetate ester is in the range 1:2.5 to 1:10 or the molar ratio of Zr to acetoacetate ester is in the range 1:45 to 1:10 and said acetoacetate ester is an ester of an alcohol containing 1 to 6 carbon atoms.
The oganometallic composition is useful in polyisocyanate compositions, particularly those used as binders for lignocellulosic materials and polyisocyanate compositions containing the organometallic compositions of the invention have good stability on storage.
The oganometallic composition is useful in polyisocyanate compositions, particularly those used as binders for lignocellulosic materials and polyisocyanate compositions containing the organometallic compositions of the invention have good stability on storage.
Description
ORGANOMETALLIC COMPOSITIONS
This invention relates to organometailic compositions based on Group IVB metals and which are useful in polyisocyanate compositions especially compositions for binding lignocellulosic material.
The use of organic polyisocyanates as binders for lignocellulosic material in the manufacture of sheets or moulded bodies such as waferboard, chipboard, fibreboard and plywood is well known. In a typical process the organic polyisocyanate, optionally in the form of a solution, dispersion or aqueous emulsion, is applied to the lignocellulosic material which is then subjected to heat and pressure.
One suitable polyisocyanate composition is disclosed in PCT Application WO 97/17388. This composition comprises a Group IVB metal compound, preferably a titanium chelate, optionally in combination with a compatibilising compound and/or conventional release agents. Although these compositions perform well as binders for lignocellulosic material and provide good release performance, it is desirable to develop a more economical composition which provides improved stability on storage before use, together with good curing properties and excellent bonding strength when applied to the lignocellulosic material.
It has now been surprisingly found that certain compounds of Group IVB
metals and acetoacetate esters can be used to cure polyisocyanate compositions and these compositions are very stable on prolonged storage and economical when used for binding lignocellulosic material.
According to the invention, an organometallic composition comprises a complex of at least one metal selected from the group consisting of titanium, zirconium and hafnium and an acetoacetate ester in which the molar ratio of Ti or Hf to acetoacetate ester is in the range 1 : 2.5 to 1:10 or the molar ratio of Zr to acetoacetate ester is in the range 1: 4.5 to 1: 10 and said acetoacetate ester is an ester of an alcohol containing 1 to 6 carbon atoms.
The titanium, zirconium or hafnium composition of the invention is described herein as a "complex". It is believed that some of the acetoacetate ester will be chemically bound to the metal (Ti, Zr or Hf) but some can be described as "free" ester. The exact proportions which are bound and free will depend partly upon the exact molar ratios present in the complex and which metal, or metals, are used, but it has been shown that the "free" ester does influence the properties, particularly the stability on storage of polyisocyanate compositions containing the complexes.
The molar ratio of titanium or hafnium to acetoacetate ester in the complex is in the range 1: 2.5 to 1: 10. When the metal is titanium, the molar ratio is preferably in the range 1: 2.5 to 1: 8 and more preferably in the range 1: 3 to 1: 6. Particularly preferred compounds have a molar ration in the range 1 4 to 1: 6. In agreement with conventional theories about the co-ordination chemistry of titanium, it is believed that two molecules of acetoacetate ester will be chemically bound to a titanium atom and the remainder will be "free". When the metal is hafnium, the molar ratio is preferably 1 : 4.5 to 1: 10 and more preferably 1 : 4.5 to 1: 8, hafnium to acetoacetate ester. When the metal is zirconium, the molar ratio is from 1: 4.5 to 1: 10 and preferably from 1: 4.5 to 1: 8, zirconium to acetoacetate ester. For hafnium or zirconium, again in accordance with conventional theory, it is believed that, for complexes which contain 4 or more moles of acetoacetate ester, 4 molecules of acetoacetate ester are chemically bound to each atom of zirconium or hafnium and the remainder are "free".
Preferably, the complex is a complex of at least one of titanium and zirconium.
This invention relates to organometailic compositions based on Group IVB metals and which are useful in polyisocyanate compositions especially compositions for binding lignocellulosic material.
The use of organic polyisocyanates as binders for lignocellulosic material in the manufacture of sheets or moulded bodies such as waferboard, chipboard, fibreboard and plywood is well known. In a typical process the organic polyisocyanate, optionally in the form of a solution, dispersion or aqueous emulsion, is applied to the lignocellulosic material which is then subjected to heat and pressure.
One suitable polyisocyanate composition is disclosed in PCT Application WO 97/17388. This composition comprises a Group IVB metal compound, preferably a titanium chelate, optionally in combination with a compatibilising compound and/or conventional release agents. Although these compositions perform well as binders for lignocellulosic material and provide good release performance, it is desirable to develop a more economical composition which provides improved stability on storage before use, together with good curing properties and excellent bonding strength when applied to the lignocellulosic material.
It has now been surprisingly found that certain compounds of Group IVB
metals and acetoacetate esters can be used to cure polyisocyanate compositions and these compositions are very stable on prolonged storage and economical when used for binding lignocellulosic material.
According to the invention, an organometallic composition comprises a complex of at least one metal selected from the group consisting of titanium, zirconium and hafnium and an acetoacetate ester in which the molar ratio of Ti or Hf to acetoacetate ester is in the range 1 : 2.5 to 1:10 or the molar ratio of Zr to acetoacetate ester is in the range 1: 4.5 to 1: 10 and said acetoacetate ester is an ester of an alcohol containing 1 to 6 carbon atoms.
The titanium, zirconium or hafnium composition of the invention is described herein as a "complex". It is believed that some of the acetoacetate ester will be chemically bound to the metal (Ti, Zr or Hf) but some can be described as "free" ester. The exact proportions which are bound and free will depend partly upon the exact molar ratios present in the complex and which metal, or metals, are used, but it has been shown that the "free" ester does influence the properties, particularly the stability on storage of polyisocyanate compositions containing the complexes.
The molar ratio of titanium or hafnium to acetoacetate ester in the complex is in the range 1: 2.5 to 1: 10. When the metal is titanium, the molar ratio is preferably in the range 1: 2.5 to 1: 8 and more preferably in the range 1: 3 to 1: 6. Particularly preferred compounds have a molar ration in the range 1 4 to 1: 6. In agreement with conventional theories about the co-ordination chemistry of titanium, it is believed that two molecules of acetoacetate ester will be chemically bound to a titanium atom and the remainder will be "free". When the metal is hafnium, the molar ratio is preferably 1 : 4.5 to 1: 10 and more preferably 1 : 4.5 to 1: 8, hafnium to acetoacetate ester. When the metal is zirconium, the molar ratio is from 1: 4.5 to 1: 10 and preferably from 1: 4.5 to 1: 8, zirconium to acetoacetate ester. For hafnium or zirconium, again in accordance with conventional theory, it is believed that, for complexes which contain 4 or more moles of acetoacetate ester, 4 molecules of acetoacetate ester are chemically bound to each atom of zirconium or hafnium and the remainder are "free".
Preferably, the complex is a complex of at least one of titanium and zirconium.
The preferred acetoacetate ester for preparing the complex is ethyl acetoacetate. The complex can be prepared from more than one acetoacetate ester but preferably only one acetoacetate ester is present in the complex.
Typically, the complexes of titanium, zirconium or hafnium are prepared from titanium, zirconium or hafnium alkoxides having the general formula M(OR)4 in which M is Ti, Zr or Hf and R is a substituted or unsubstituted, cyclic or linear, alkyl, alkenyl, aryl or alkyl-aryl group or mixtures thereof.
Preferably, R
contains up to 8 carbon atoms and, more preferably, up to 6 carbon atoms.
Generally, all four OR groups will be identical but alkoxides derived from a mixture of alcohols can be used and mixtures of alkoxides can be employed when more than one metal is present in the complex. Suitable alkoxides include tetramethoxytitanium, tetra-ethoxytitanium, tetra-isopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, tetrakis(2-ethylhexoxy)titanium, tetrakis(2-ethoxyethoxy)titanium, tetracyclohexyloxytitanium, tetraphenoxy-titanium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetra-n-propoxyhafnium and tetra-n-butoxyhafnium.
Alternatively, the complex can be prepared from condensed alkoxides of titanium, zirconium or hafnium. These compounds can be represented by the general formula RO[M(OR)20]xR, wherein M and R have the same meaning as discussed above and x is an integer. Generally, these condensed alkoxides consist of a mixture containing compounds of the above formula with x having a range of values. Preferably, x has an average value in the range 2 to 16 and, more preferably, in the range 2 to 8. A condensed alkoxide is usually prepared by the controlled addition of water to an alkoxide, followed by removal of alcohol which is displaced. Suitable condensed alkoxides include the compounds known as polybutyl titanate, polybutyl zirconate and polyisopropyl titanate.
Complexes of condensed alkoxides can also be prepared by forming a complex of an acetoacetate ester with an alkoxide, adding water to the complex and removing any by-product alcohol.
Other titanium, zirconium or hafnium compounds, such as titanium, zirconium or hafnium tetrachloride or alkoxides which have been substituted with, for example, glycol or phosphorus substituents can be used as raw materials for the formation of the complex used in the invention.
The complex can be readily prepared by mixing, for example, an alkoxide or condensed alkoxide with an appropriate amount of acetoacetate ester.
Alcohol from the alkoxide will be displaced by the acetoacetate ester and, preferably, the displaced alcohol is removed by, for example, distillation. In a preferred method, 2 moles of acetoacetate ester per atom of Ti or 4 moles of acetoacetate ester per atom of Zr or Hf are added to an alkoxide or condensed alkoxide and the displaced alcohol is removed by distillation. Any additional acetoacetate ester required is then added to the stripped product. This method is advantageous because it provides a consistent product of known stoichiometry. It is possible to add all the acetoacetate ester in one charge and subsequently remove all the displaced alcohol but some of the "free"
acetoacetate ester is usually accidentally removed during this process, leading to inconsistent products and contamination of the displaced alcohol.
Altematively, when an organometallic composition according to the invention is used in a polyisocyanate composition, a product containing, for example, 2 moles of acetoacetate ester per Ti atom or 4 moles of acetoacetate ester per Zr or Hf atom can be prepared according to the method outlined above and this can be mixed with a polyisocyanate. Any additional acetoacetate ester required to produce the organometallic composition of the invention can be added to the polyisocyanate before or after the titanium, zirconium or hafnium compound has been added. This effectively results in the preparation of an organometallic composition according to this invention in situ in the polyisocyanate composition. Other methods of preparing the composition of the invention will be apparent to a person skilled in this art.
The organometallic complexes of the invention are particularly useful as 5 curing agents in polyisocyanate compositions and compositions suitable for use with the organometallic compositions of the present invention may be any organic poiyisocyanate compound or mixture of organic polyisocyanate compounds, provided said compounds have at least 2 isocyanate groups.
Organic polyisocyanates include diisocyanates, particularly aromatic diisocyanates, and isocyanates of higher functionality.
Examples of organic polyisocyanates for which the organometallic complexes of the present invention are useful curing agents include aliphatic isocyanates such as hexamethylene diisocyanate; and aromatic isocyanates such as m- and p-phenylene diisocyanate, tolylene-2,4- and tolyiene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, chlorophenyiene-2,4-diisocyanate, naphthylene-1,5-diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl-diphenyl, 3-methyidiphenylmethane-4,4'-di-isocyanate and diphenyl ether diisocyanate; and cycloaliphatic diisocyanates such as cyclohexane-2,4- and -2,3-diisocyanate, 1-methylcycfohexyl-2,4- and -2,6-diisocyanate and mixtures thereof and bis-(isocyanatocyclohexyl)methane and triisocyanates such as 2,4,6-triisocyanatotoluene and 2,4,4-tri-isocyanatodiphenylether.
Modified polyisocyanates containing isocyanurate, carbodiimide or uretonimine groups may be employed in conjunction with the organometallic complexes of the invention as well. Further blocked polyisocyanates, like the reaction product of a phenol or an oxime and a polyisocyanate, may be used, having a deblocking temperature below the temperature applied when using a polyisocyanate composition.
The organic polyisocyanate useful with the organometallic composition of the invention may also be an isocyanate-ended prepolymer made by reacting an excess of a diisocyanate or higher functionality polyisocyanate with a polyol.
Water-emulsifiable organic polyisocyanates like those described in UK
patent no. 1 444 933, in European patent publication no. 516 361 and in PCT
patent pubfication no. 93/03082 can also be used.
Mixtures of isocyanates may be used in conjunction with the organometallic composition of the invention, for example a mixture of tolyiene diisocyanate isomers such as the commercially available mixtures of 2,4- and 2,6-isomers and also the mixture of di- and higher polyisocyanates.
Polyisocyanate mixtures may optionally contain monofunctional isocyanates such as p-ethyl phenylisocyanate.
Such mixtures are well-known in the art and include the crude phosgenation products containing methylene bridged polyphenyl polyisocyanates, including diisocyanate, triisocyanate and higher polyisocyanates together with any phosgenation by-products.
Preferred isocyanates to be used in conjunction with the organometallic complexes of the present invention are those wherein the isocyanate is an aromatic diisocyanate or polyisocyanate of higher functionality such as a pure diphenyimethane diisocyanate or a mixture of methylene bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanates and higher functionality polyisocyanates.
Methylene bridged polyphenyl polyisocyanates are well known in the art.
They are prepared by phosgenation of corresponding mixtures of polyamines.
For convenience, polymeric mixtures of inethylene bridged polyphenyl polyisocyanates containing diisocyanate, triisocyanate and higher functionality polyisocyanates are referred to hereinafter as polymeric MDI. Polyisocyanates suitable for use with the organometallic complexes of the invention include SUPRASECTM DNR, SUPRASECTM 2185, RUBINATETM M and RUBINATETM
1840, all available from Imperial Chemical Industries.
Preferably the polyisocyanate is liquid at room temperature.
Conventional release agents can be added to or used in combination with a polyisocyanate composition containing a titanium, zirconium or hafnium complex of an acetoacetate ester according to the present invention.
In such compositions the conventional release agent is present in an amount varying between 0.2 and 10 %, preferably between 0.5 and 6 % and most preferably between 1 and 3 % by weight based on the polyisocyanate whereas the titanium, zirconium or hafnium complex of an acetoacetate ester is preferably present in an amount varying between 0.2 and 4%a, most preferably between 0.2 and 2 % by weight based on the polyisocyanate.
Examples of conventional release agents include polysiloxanes, saturated or unsaturated fatty acids (such as oleic acid) or fatty acid amides or fatty acid esters and polyolefin waxes.
Preferred conventional release agents to be used in ' polyisocyanate compositions containing the organometallic complexes according to the present invention are polyolefin waxes or mixtures of polyolefin waxes, especially functionalised polyolefin waxes, which are dispersible in an aqueous medium to form an aqueous emulsion. More preferably, the polyolefin waxes are selected from oxidised polyethylene waxes and oxidised polypropylene waxes.
A preferred method for using the release agent is to apply the emulsion to the surface of the poiyisocyanate treated lignocellulosic material or to the press metal surface prior to hot pressing the combination.
Typically, the complexes of titanium, zirconium or hafnium are prepared from titanium, zirconium or hafnium alkoxides having the general formula M(OR)4 in which M is Ti, Zr or Hf and R is a substituted or unsubstituted, cyclic or linear, alkyl, alkenyl, aryl or alkyl-aryl group or mixtures thereof.
Preferably, R
contains up to 8 carbon atoms and, more preferably, up to 6 carbon atoms.
Generally, all four OR groups will be identical but alkoxides derived from a mixture of alcohols can be used and mixtures of alkoxides can be employed when more than one metal is present in the complex. Suitable alkoxides include tetramethoxytitanium, tetra-ethoxytitanium, tetra-isopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, tetrakis(2-ethylhexoxy)titanium, tetrakis(2-ethoxyethoxy)titanium, tetracyclohexyloxytitanium, tetraphenoxy-titanium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetra-n-propoxyhafnium and tetra-n-butoxyhafnium.
Alternatively, the complex can be prepared from condensed alkoxides of titanium, zirconium or hafnium. These compounds can be represented by the general formula RO[M(OR)20]xR, wherein M and R have the same meaning as discussed above and x is an integer. Generally, these condensed alkoxides consist of a mixture containing compounds of the above formula with x having a range of values. Preferably, x has an average value in the range 2 to 16 and, more preferably, in the range 2 to 8. A condensed alkoxide is usually prepared by the controlled addition of water to an alkoxide, followed by removal of alcohol which is displaced. Suitable condensed alkoxides include the compounds known as polybutyl titanate, polybutyl zirconate and polyisopropyl titanate.
Complexes of condensed alkoxides can also be prepared by forming a complex of an acetoacetate ester with an alkoxide, adding water to the complex and removing any by-product alcohol.
Other titanium, zirconium or hafnium compounds, such as titanium, zirconium or hafnium tetrachloride or alkoxides which have been substituted with, for example, glycol or phosphorus substituents can be used as raw materials for the formation of the complex used in the invention.
The complex can be readily prepared by mixing, for example, an alkoxide or condensed alkoxide with an appropriate amount of acetoacetate ester.
Alcohol from the alkoxide will be displaced by the acetoacetate ester and, preferably, the displaced alcohol is removed by, for example, distillation. In a preferred method, 2 moles of acetoacetate ester per atom of Ti or 4 moles of acetoacetate ester per atom of Zr or Hf are added to an alkoxide or condensed alkoxide and the displaced alcohol is removed by distillation. Any additional acetoacetate ester required is then added to the stripped product. This method is advantageous because it provides a consistent product of known stoichiometry. It is possible to add all the acetoacetate ester in one charge and subsequently remove all the displaced alcohol but some of the "free"
acetoacetate ester is usually accidentally removed during this process, leading to inconsistent products and contamination of the displaced alcohol.
Altematively, when an organometallic composition according to the invention is used in a polyisocyanate composition, a product containing, for example, 2 moles of acetoacetate ester per Ti atom or 4 moles of acetoacetate ester per Zr or Hf atom can be prepared according to the method outlined above and this can be mixed with a polyisocyanate. Any additional acetoacetate ester required to produce the organometallic composition of the invention can be added to the polyisocyanate before or after the titanium, zirconium or hafnium compound has been added. This effectively results in the preparation of an organometallic composition according to this invention in situ in the polyisocyanate composition. Other methods of preparing the composition of the invention will be apparent to a person skilled in this art.
The organometallic complexes of the invention are particularly useful as 5 curing agents in polyisocyanate compositions and compositions suitable for use with the organometallic compositions of the present invention may be any organic poiyisocyanate compound or mixture of organic polyisocyanate compounds, provided said compounds have at least 2 isocyanate groups.
Organic polyisocyanates include diisocyanates, particularly aromatic diisocyanates, and isocyanates of higher functionality.
Examples of organic polyisocyanates for which the organometallic complexes of the present invention are useful curing agents include aliphatic isocyanates such as hexamethylene diisocyanate; and aromatic isocyanates such as m- and p-phenylene diisocyanate, tolylene-2,4- and tolyiene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, chlorophenyiene-2,4-diisocyanate, naphthylene-1,5-diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl-diphenyl, 3-methyidiphenylmethane-4,4'-di-isocyanate and diphenyl ether diisocyanate; and cycloaliphatic diisocyanates such as cyclohexane-2,4- and -2,3-diisocyanate, 1-methylcycfohexyl-2,4- and -2,6-diisocyanate and mixtures thereof and bis-(isocyanatocyclohexyl)methane and triisocyanates such as 2,4,6-triisocyanatotoluene and 2,4,4-tri-isocyanatodiphenylether.
Modified polyisocyanates containing isocyanurate, carbodiimide or uretonimine groups may be employed in conjunction with the organometallic complexes of the invention as well. Further blocked polyisocyanates, like the reaction product of a phenol or an oxime and a polyisocyanate, may be used, having a deblocking temperature below the temperature applied when using a polyisocyanate composition.
The organic polyisocyanate useful with the organometallic composition of the invention may also be an isocyanate-ended prepolymer made by reacting an excess of a diisocyanate or higher functionality polyisocyanate with a polyol.
Water-emulsifiable organic polyisocyanates like those described in UK
patent no. 1 444 933, in European patent publication no. 516 361 and in PCT
patent pubfication no. 93/03082 can also be used.
Mixtures of isocyanates may be used in conjunction with the organometallic composition of the invention, for example a mixture of tolyiene diisocyanate isomers such as the commercially available mixtures of 2,4- and 2,6-isomers and also the mixture of di- and higher polyisocyanates.
Polyisocyanate mixtures may optionally contain monofunctional isocyanates such as p-ethyl phenylisocyanate.
Such mixtures are well-known in the art and include the crude phosgenation products containing methylene bridged polyphenyl polyisocyanates, including diisocyanate, triisocyanate and higher polyisocyanates together with any phosgenation by-products.
Preferred isocyanates to be used in conjunction with the organometallic complexes of the present invention are those wherein the isocyanate is an aromatic diisocyanate or polyisocyanate of higher functionality such as a pure diphenyimethane diisocyanate or a mixture of methylene bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanates and higher functionality polyisocyanates.
Methylene bridged polyphenyl polyisocyanates are well known in the art.
They are prepared by phosgenation of corresponding mixtures of polyamines.
For convenience, polymeric mixtures of inethylene bridged polyphenyl polyisocyanates containing diisocyanate, triisocyanate and higher functionality polyisocyanates are referred to hereinafter as polymeric MDI. Polyisocyanates suitable for use with the organometallic complexes of the invention include SUPRASECTM DNR, SUPRASECTM 2185, RUBINATETM M and RUBINATETM
1840, all available from Imperial Chemical Industries.
Preferably the polyisocyanate is liquid at room temperature.
Conventional release agents can be added to or used in combination with a polyisocyanate composition containing a titanium, zirconium or hafnium complex of an acetoacetate ester according to the present invention.
In such compositions the conventional release agent is present in an amount varying between 0.2 and 10 %, preferably between 0.5 and 6 % and most preferably between 1 and 3 % by weight based on the polyisocyanate whereas the titanium, zirconium or hafnium complex of an acetoacetate ester is preferably present in an amount varying between 0.2 and 4%a, most preferably between 0.2 and 2 % by weight based on the polyisocyanate.
Examples of conventional release agents include polysiloxanes, saturated or unsaturated fatty acids (such as oleic acid) or fatty acid amides or fatty acid esters and polyolefin waxes.
Preferred conventional release agents to be used in ' polyisocyanate compositions containing the organometallic complexes according to the present invention are polyolefin waxes or mixtures of polyolefin waxes, especially functionalised polyolefin waxes, which are dispersible in an aqueous medium to form an aqueous emulsion. More preferably, the polyolefin waxes are selected from oxidised polyethylene waxes and oxidised polypropylene waxes.
A preferred method for using the release agent is to apply the emulsion to the surface of the poiyisocyanate treated lignocellulosic material or to the press metal surface prior to hot pressing the combination.
When used, an aqueous emulsion of the polyolefin wax should normally contain a sufficient amount of the polyolefin wax to provide a coverage of about 0.01 to about 1, and preferably about 0.02 to about 0.5 mg of the polyolefin wax per cml of lignocellulosic material or press metal surface. Generally, lower levels of polyolefin wax are preferred as they are more cost effective. When taking the emulsifiers into account, the aqueous emulsions will usually contain about 0.2 to about 10 %, preferably about 0.3 to about 5 % by weight of total solids. The emulsions are usually prepared at 30 to 40 % total solids, transported to the point of use and then diluted with water to the desired concentration.
It has been found that the polyolefin wax emulsion, when used in combination with polyisocyanate compositions containing organometallic compositions of the present invention, may be usefully applied to the lignocellulosic material or press metal surface in an amount equivalent to 8 to 14 mg per cmZ.
A particularly preferred polyethylene wax emulsion which can be used in a process in combination with an organometallic composition of the present invention in combination with a polyisocyanate is RubilonT'" 603 or RubilonTM
605, both available from Imperial Chemical Industries.
A particularly preferred polypropylene wax emulsion which can be used in a process in combination with an organometallic composition of the present invention in combination with a polyisocyanate is ME 42040*available from Micheiman Inc. of Cincinnati, Ohio.
In order to further improve the storage stability of a polyisocyanate composition containing an organometallic composition of the present invention a diluent may be added to the composition. Suitable diluents include plasticizers of the type mentioned in "Taschenbuch der Kunststoff-Additive", Ed. by R.
* Trade Mark Gachter and H. Muller, Carl Hanser Verlag Munchen, third edition, 1989.
Preferred diluents are phthalates, aliphatic carboxylates, fatty acid esters, linseed oil and soybean oil. A particularly preferred diluent is Priolube 1403*
available from Unichema being methyloleate. These diluents are added in amounts of from 1 to 40 parts by weight per 100 parts by weight of polyisocyanate and preferably in amounts of from 1 to 15 parts by weight per 100 parts by weight of polyisocyanate.
A composition containing an organometallic composition of the present invention and a polyisocyanate may further comprise conventional additives like flame retardants, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, surfactants, thixotropic agents and other binders like formaldehyde condensate adhesive resins and lignin (optionally in combination with a lignin solvent such as described in PCT Patent Application No.
EP96/00924).
A particularly preferred additive to be used in a polyisocyanate composition containing an organometallic composition of the present invention is a coupling agent such as an organofunctional silane (for example, Dynasyian AMEO* available from Huels). Adding such a coupling agent to the polyisocyanate composition leads to improved board properties. The organofunctional silane coupling agents are used in amounts ranging from 0.01 to 3 %, preferably from 0.1 to 2 % by weight based on the polyisocyanate.
The organometallic composition of present invention can be used in a process for preparing lignocellulosic bodies by bringing lignocellulosic parts into contact with a polyisocyanate composition containing the organometallic composition of the present invention and pressing this combination.
* Trade Mark A typicai process comprises the steps of a) bringing said lignocellulosic material in contact with a polyisocyanate composition containing an organometallic composition of the present invention and, 5 b) subsequently allowing said material to bind.
The lignocelluiosic bodies are prepared by bringing the lignocellulosic parts into contact with a polyisocyanate composition by means such as mixing, spraying and/or spreading the composition with/onto the lignocellulosic parts and by pressing the combination of the polyisocyanate composition and the 10 lignocellulosic parts, preferably by hot-pressing, normally at 150 C to and 2 to 6 MPa specific pressure.
Such binding processes are commonly known in the art.
In waferboard manufacture the lignocellulosic material and the polyisocyanate composition may be conveniently mixed by spraying the present poiyisocyanate composition on the lignocellulosic material while it is being agitated.
As described hereinbefore, in a preferred process, a release agent, which is preferably an aqueous emulsion of a polyolefin wax, is appiied to the surface of the polyisocyanate treated lignocellulosic material or to the press metal surface prior to hot pressing the combination.
The lignocellulosic material after treatment with the polyisocyanate composition containing an organometallic composition according to the invention is placed on caul plates made of aluminium or steel which serve to carry the furnish into the press where it is compressed to the desired extent usually at a temperature between 150 C and 250 C.
While the process is particularly suitable for the manufacture of waferboard known extensively as oriented strand board and will be largely used for such manufacture, the process may not be regarded as limited in this respect and can also be used in the manufacture of medium density fibreboard, particle board (also known as chipboard) and plywood.
Thus the lignocellulosic material used can include wood strands, woodchips, wood fibres, shavings, veneers, wood wool, cork, bark, sawdust and like waste products of the wood working industry as well as other materials having a lignocellulosic basis such as paper, bagasse, straw, flax, sisal, hemp, rushes, reeds, rice hulls, husks, grass, nutshelis and the like. Additionally, there may be mixed with the lignocellulosic materials other particulate or fibrous materials such as ground foam waste (for example, ground polyurethane foam waste), mineral fillers, glass fibre, mica, rubber, textile waste such as plastic fibres and fabrics.
When the polyisocyanate composition containing the organometallic composition of the invention is applied to the lignocellulosic material, the weight ratio of polyisocyanate/lignocellulosic material will vary depending on the bulk density of the lignocellulosic material employed. Therefore, the polyisocyanate compositions may be applied in such amounts to give a weight ratio of polyisocyanate/lignocellulosic material in the range of 0.1 : 99.9 to 20 : 80 and preferably in the range of 0.5 : 99.5 to 10 : 90.
If desired, other conventional binding agents, such as formaldehyde condensate adhesive resins, may be used in conjunction with the polyisocyanate composition containing the organometallic composition.
More detailed descriptions of methods of manufacturing waferboard and similar products based on lignoceiiulosic material are available in the prior art.
The techniques and equipment conventionally used can be adapted for use with polyisocyanate compositions containing organometallic compositions of the present invention.
It has been found that the polyolefin wax emulsion, when used in combination with polyisocyanate compositions containing organometallic compositions of the present invention, may be usefully applied to the lignocellulosic material or press metal surface in an amount equivalent to 8 to 14 mg per cmZ.
A particularly preferred polyethylene wax emulsion which can be used in a process in combination with an organometallic composition of the present invention in combination with a polyisocyanate is RubilonT'" 603 or RubilonTM
605, both available from Imperial Chemical Industries.
A particularly preferred polypropylene wax emulsion which can be used in a process in combination with an organometallic composition of the present invention in combination with a polyisocyanate is ME 42040*available from Micheiman Inc. of Cincinnati, Ohio.
In order to further improve the storage stability of a polyisocyanate composition containing an organometallic composition of the present invention a diluent may be added to the composition. Suitable diluents include plasticizers of the type mentioned in "Taschenbuch der Kunststoff-Additive", Ed. by R.
* Trade Mark Gachter and H. Muller, Carl Hanser Verlag Munchen, third edition, 1989.
Preferred diluents are phthalates, aliphatic carboxylates, fatty acid esters, linseed oil and soybean oil. A particularly preferred diluent is Priolube 1403*
available from Unichema being methyloleate. These diluents are added in amounts of from 1 to 40 parts by weight per 100 parts by weight of polyisocyanate and preferably in amounts of from 1 to 15 parts by weight per 100 parts by weight of polyisocyanate.
A composition containing an organometallic composition of the present invention and a polyisocyanate may further comprise conventional additives like flame retardants, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, surfactants, thixotropic agents and other binders like formaldehyde condensate adhesive resins and lignin (optionally in combination with a lignin solvent such as described in PCT Patent Application No.
EP96/00924).
A particularly preferred additive to be used in a polyisocyanate composition containing an organometallic composition of the present invention is a coupling agent such as an organofunctional silane (for example, Dynasyian AMEO* available from Huels). Adding such a coupling agent to the polyisocyanate composition leads to improved board properties. The organofunctional silane coupling agents are used in amounts ranging from 0.01 to 3 %, preferably from 0.1 to 2 % by weight based on the polyisocyanate.
The organometallic composition of present invention can be used in a process for preparing lignocellulosic bodies by bringing lignocellulosic parts into contact with a polyisocyanate composition containing the organometallic composition of the present invention and pressing this combination.
* Trade Mark A typicai process comprises the steps of a) bringing said lignocellulosic material in contact with a polyisocyanate composition containing an organometallic composition of the present invention and, 5 b) subsequently allowing said material to bind.
The lignocelluiosic bodies are prepared by bringing the lignocellulosic parts into contact with a polyisocyanate composition by means such as mixing, spraying and/or spreading the composition with/onto the lignocellulosic parts and by pressing the combination of the polyisocyanate composition and the 10 lignocellulosic parts, preferably by hot-pressing, normally at 150 C to and 2 to 6 MPa specific pressure.
Such binding processes are commonly known in the art.
In waferboard manufacture the lignocellulosic material and the polyisocyanate composition may be conveniently mixed by spraying the present poiyisocyanate composition on the lignocellulosic material while it is being agitated.
As described hereinbefore, in a preferred process, a release agent, which is preferably an aqueous emulsion of a polyolefin wax, is appiied to the surface of the polyisocyanate treated lignocellulosic material or to the press metal surface prior to hot pressing the combination.
The lignocellulosic material after treatment with the polyisocyanate composition containing an organometallic composition according to the invention is placed on caul plates made of aluminium or steel which serve to carry the furnish into the press where it is compressed to the desired extent usually at a temperature between 150 C and 250 C.
While the process is particularly suitable for the manufacture of waferboard known extensively as oriented strand board and will be largely used for such manufacture, the process may not be regarded as limited in this respect and can also be used in the manufacture of medium density fibreboard, particle board (also known as chipboard) and plywood.
Thus the lignocellulosic material used can include wood strands, woodchips, wood fibres, shavings, veneers, wood wool, cork, bark, sawdust and like waste products of the wood working industry as well as other materials having a lignocellulosic basis such as paper, bagasse, straw, flax, sisal, hemp, rushes, reeds, rice hulls, husks, grass, nutshelis and the like. Additionally, there may be mixed with the lignocellulosic materials other particulate or fibrous materials such as ground foam waste (for example, ground polyurethane foam waste), mineral fillers, glass fibre, mica, rubber, textile waste such as plastic fibres and fabrics.
When the polyisocyanate composition containing the organometallic composition of the invention is applied to the lignocellulosic material, the weight ratio of polyisocyanate/lignocellulosic material will vary depending on the bulk density of the lignocellulosic material employed. Therefore, the polyisocyanate compositions may be applied in such amounts to give a weight ratio of polyisocyanate/lignocellulosic material in the range of 0.1 : 99.9 to 20 : 80 and preferably in the range of 0.5 : 99.5 to 10 : 90.
If desired, other conventional binding agents, such as formaldehyde condensate adhesive resins, may be used in conjunction with the polyisocyanate composition containing the organometallic composition.
More detailed descriptions of methods of manufacturing waferboard and similar products based on lignoceiiulosic material are available in the prior art.
The techniques and equipment conventionally used can be adapted for use with polyisocyanate compositions containing organometallic compositions of the present invention.
Polyisocyanate compositions containing organometatlic compositions of the present invention are extremely effective in minimising unwanted adhesion to caul plates, press plates and other surfaces with which the treated lignocellulosic material may come into contact. Their storage stability and 5. release performance is improved compared to polyisocyanate compositions of the prior art, as well as the obtained board properties.
The sheets and moulded bodies produced from the polyisocyanate compositions containing organometallic compositions of the present invention have excellent mechanical properties and they may be used in any of the situations where such articles are customarily used.
The invention is illustrated but not limited by the following examples.
Preparation of Product A
A reactor was charged with tetraisopropyl titanate (1400 kg, Tilcom* TIPT
from ICI Vertec). Ethylacetoacetate (1282 kg) was then added with stirring.
The resulting product was a pale red liquid. The displaced alcohol (580 kg, isopropanol) was then removed by evaporation to leave a red liquid, PRODUCT
A (2090 kg).
Product A was then diluted by addition of various amounts of methyfacetoacetate, ethylacetoacetate and cetylacetoacetate in the following molar ratios.
* Trade Mark TABLE I
Sample Moles Product A Moles Methylacetoacetate Test 1 1 1.1 Test 2 1 2.2 Test 3 1 4.4 Test 4 1 6.6 Test 5 1 8.8 Test 6 1 11 Sample Moles Product A Moles Ethylacetoacetate Test 7 1 1.1 Test 8 1 2.2 Test 9 1 4.4 Test 10 1 6.6 Test 11 1 8.8 Test 12 1 11 Sample Moles Product A Moles Cetylacetoacetate Comparison 1 1.1 Comparison 2 1 2.2 Comparison 3 4.4 Comparison 4 1 6.6 Comparison 5 1 8.8 Comparison 6 1 11 The products were evaluated by preparing a number of compositions comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC
DNR*available from Imperial Chemical Industries) and various amounts of the samples designated Test 1 to 12 (see Table 4 below). Each composition contained the same concentration of Product A. The compositions were then stored at 45 C and the viscosity tested by means of a Brookfield viscometer at various intervals.
* Trade Mark Sample Parts by weight Parts by weight Suprasec DNR
Test 1 0.78 100 Test 2 0.96 100 Test 3 1.32 100 Test 4 1.67 100 Test 5 2.03 100 Test 6 2.38 100 Test 7 0.80 100 Test 8 1.00 100 Test 9 1.40 100 Test 10 1.80 100 Test 11 2.20 100 Test 12 2.60 100 As a comparison a number of compositions comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and various amounts of the samples designated 5 Comparison 1 to 6 (see Table 5 below) were made up. All these compositions contained the same amount of Product A, this amount being the same as the amount of Product A in each of the compositions designated Test 1 to Test 12.
These compositions were then stored at 450 C and the viscosity tested using a Brookfield viscometer at the same intervals.
Sample Parts by weight Parts by weight Suprasec DNR
Comparison 1 1.1 100 Comparison 2 1.6 100 Comparison 3 2.6 100 Comparison 4 3.6 100 Comparison 5 4.6 100 Comparison 6 5.6 100 The following results were obtained for the systems based on Product A
with various added amounts of methylacetoacetate and ethylacetoacetate [all results are reported in Pa s].
Product A + Methy/acetoacetate Time Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 (Days) 0 0.292 0.288 0.274 0.272 0.267 0.267 14 0.828 0.548 0.632 0.678 0.746 0.806 25 1.208 0.734 0.840 1.007 1.078 1.153 30 n.m. 1.050 1.139 1.330 1.526 1.756 46 2.568 1.207 1.239 1.546 1.767 2.125 67 n.m. 1.917 1.707 2.209 2.579 3.392 n.m. = not measured Product A + Ethylacetoacetate Time Test 7 Test 8 Test 9 Test 10 Test 11 Test 12 (Days) 0 0.305 0.293 0.280 0.270 0.263 0.263 14 0.787 0.600 0.645 0.717 0.806 0.814 25 1.136 0.879 0.911 1.078 1.197 1.251 30 n.m. 1.137 1.225 1.538 1.734 1.811 46 2.486 1.310 1.410 1.735 2.240 2.018 67 n.m. 2.028 1.943 2.440 3.275 3.192 n.m. = not measured The following results were obtained for the systems based on Product A
with various added amounts of cetylacetoacetate [all results reported in Pa s].
Product A + Cetylacetoacetate Time Comparison Comparison Comparison Comparison Comparison Comparison (Days) 1 2 3 4 5 6 0 0.324 0.296 0.296 0.277 0.279 0.264 14 1.195 0.599 0.627 0.630 0.667 0.626 25 1.995 0.797 0.839 0.851 1.014 0.989 30 n.m. 1.145 1.168 1.049 1.430 1.427 46 4.620 1.396 1.281 1.162 1.608 1.620 67 n.m. 2.443 1.853 1.610 2.260 2.309 n. m. = not measured Generally, the most relevant period for storage stability at room temperature is the period 14 to 46 days after production of a polyisocyanate composition. From Tables 6 to 8 above, it can be seen that the optimum (generally, lowest) viscosity after 46 days at 45 C (an accelerated test) is achieved in Test 2 (2.2 moles methylacetoacetate), Test 8 (2.2 moles ethylacetoacetate) and Comparison 4 (6.6 moles cetylacetoacetate). The results demonstrate that the titanium complexes used in the composition of the invention provide a more economical means of stabilising the polyisocyanate composition.
Preparation of Product B
A flask was charged with tetra-n-propyl zirconate (43.7g, Tilcom` NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a cold water bath. Methylacetoacetate (46.5g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a paie yellow liquid. The displaced alcohol (35.3g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (54.8g). The oil was then mixed with additional methylacetoacetate (11.6g) to yield PRODUCT B.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.09 parts by weight Product B was prepared in duplicate. The compositions were then stored at 450 C and the viscosity tested at various intervais using a Brookfield viscometer. Results are reported in Table 9 below in Pa s.
Time (Days) Product B(i) Product B(ii) 0 0.220 0.220 20 0.440 0.400 41 0.580 0.520 62 0.660 0.640 84 1.020 1.340 Preparation of Product C
A flask was charged with tetra-n-propyl zirconate (43.7g, Tilcom" NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a cold water bath. Methylacetoacetate (46.5g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (34.3g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (55.8g). The oil was then mixed with additional methylacetoacetate (23.2g) to yield PRODUCT C.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.48 parts by weight Product C was prepared in duplicate. The compositions were then stored at 45 C and the viscosity tested at various intervals using a Brookfield viscometer. Results are reported in Table 10 below in Pa s.
Time (Days) Product C(i) Product C(ii) 0 0.220 0.220 20 0.460 0.500 41 0.500 0.500 62 0.720 0.620 84 1.280 0.980 Preparation of Product D
A flask was charged with tetra-n-propyl zirconate (87.3g, Tilcom" NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a 5 cold water bath. Ethylacetoacetate (104g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid.
The displaced alcohol (67.1 g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (1 24.3g). The oil was then mixed with additional ethyl acetoacetate (26g) to yield PRODUCT D.
10 To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.21 parts by weight Product D was prepared in duplicate. The compositions were then stored at 45 C and the viscosity of the compositions tested at various intervals using a Brookfield viscometer.
Results 15 are reported in Table 11 below in Pa s.
Time (Days) Product D(i) Product D(ii) 0 0.220 0.220 20 0.480 0.460 41 0.540 0.560 62 0.700 0.920 84 1.140 1.040 Prenaration of Product E
A flask was charged with tetra-n-propyl zirconate (87.3g, Tilcom" NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (104g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid.
The displaced aicohol (70.0g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (121.4g). The oil was then mixed with additional ethylacetoacetate (52g) to yield PRODUCT E.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.56 parts by weight Product E was prepared in duplicate. The compositions were then stored at 450 C and the viscosity of the compositions tested at various intervals using a Brookfield viscometer.
Results are reported in Table 12 below in Pa s.
Time (Days) Product E(i) Product E(ii) 0 0.220 0.220 20 0.560 0.580 41 0.620 0.600 62 0.860 0.780 84 1.060 0.960 The zirconium complexes (Products B, C, D E) show improved stability over a longer period of time than the titanium complexes of Comparison 1 to 6 (Table 8).
Prenaration of Product F
A flask was charged with tetraisopropyl titanate (71 g, Tilcom` TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, distilled water (1.1g, 0.25 moles per mole Ti) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (43.4g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (94.5g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT F.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 0.88 parts by weight Product F was prepared. The composition was then stored at 45 C and the viscosity of the composition tested at various intervais using a Brookfield viscometer.
Preoaration of Product G
A flask was charged with tetraisopropyl titanate (71 g, TilcomA TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, distilled water (2.3g, 0.5 moles per mole of Ti) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (48.4g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (93.3g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT G.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 0.88 parts by weight Product G was prepared. The composition was then stored at 45 C and the viscosity of the composition tested at various intervals using a Brookfield viscometer. Results are reported for Product F and Product G in Table 13 below in Pa s.
Time (Days) Product F Product G
0 0.220 0.220 10 0.485 0.520 40 0.760 0.760 60 1.100 1.200 80 1.140 1.220 A flask was charged with tetraisopropyl titanate (71g, Tilcom' TIPT from ICI Vertec) and placed in a cold water bath. tert-Butylacetoacetate (79.1 g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (30.0g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (120.0g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT H.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 1.02 parts by weight Product H was prepared. The composition was then stored at 450 C and the viscosity of the composition tested at various intervals using a Brookfield viscometer. Results are reported in Table 14 below in Pa s.
Time (Days) Viscosity 0 ` 0.220 10 0.480 40 1.160 60 1.800 80 2.160 Preoaration of Product I
A flask was charged with tetraisopropyl titanate (71g, Tilcoma TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added 5 over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, butyl acid phosphate (11.4g, 0.25 moles) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (38.2g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (109.2g). This liquid was then mixed with additional ethyl 10 acetoacetate (65g) to yield PRODUCT I.
To evaiuate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical lndustries) and 0.97 parts by weight Product I was prepared in duplicate. The compositions were then stored at 45 C and the viscosity of the 15 compositions tested at various intervals using a Brookfield viscometer (see Table 15).
Preparation of Product J
A flask was charged with tetraisopropyl titanate (71 g, Tilcom` TIPT from ICI Vertec) and placed in a cold water bath. Ethyiacetoacetate (65g) was added 20 over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, butyl acid phosphate (22.8g, 0.5 moles) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (40.8g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (118.0g). This liquid was then mixed with additional ethyl 25 acetoacetate (65g) to yield PRODUCT J.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 1.02 parts by weight Product J was prepared. The composition was then stored at 45 C and the viscosity of the composition tested at various intervals using a Brookfield viscometer. Results are reported for Product I and Product J in Table 15 below in Pa s.
Time (Days) Product I Product J
0 0.220 0.220 0.440 0.389 40 0.880 0.580 60 1.320 0.960 80 1.360 1.040
The sheets and moulded bodies produced from the polyisocyanate compositions containing organometallic compositions of the present invention have excellent mechanical properties and they may be used in any of the situations where such articles are customarily used.
The invention is illustrated but not limited by the following examples.
Preparation of Product A
A reactor was charged with tetraisopropyl titanate (1400 kg, Tilcom* TIPT
from ICI Vertec). Ethylacetoacetate (1282 kg) was then added with stirring.
The resulting product was a pale red liquid. The displaced alcohol (580 kg, isopropanol) was then removed by evaporation to leave a red liquid, PRODUCT
A (2090 kg).
Product A was then diluted by addition of various amounts of methyfacetoacetate, ethylacetoacetate and cetylacetoacetate in the following molar ratios.
* Trade Mark TABLE I
Sample Moles Product A Moles Methylacetoacetate Test 1 1 1.1 Test 2 1 2.2 Test 3 1 4.4 Test 4 1 6.6 Test 5 1 8.8 Test 6 1 11 Sample Moles Product A Moles Ethylacetoacetate Test 7 1 1.1 Test 8 1 2.2 Test 9 1 4.4 Test 10 1 6.6 Test 11 1 8.8 Test 12 1 11 Sample Moles Product A Moles Cetylacetoacetate Comparison 1 1.1 Comparison 2 1 2.2 Comparison 3 4.4 Comparison 4 1 6.6 Comparison 5 1 8.8 Comparison 6 1 11 The products were evaluated by preparing a number of compositions comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC
DNR*available from Imperial Chemical Industries) and various amounts of the samples designated Test 1 to 12 (see Table 4 below). Each composition contained the same concentration of Product A. The compositions were then stored at 45 C and the viscosity tested by means of a Brookfield viscometer at various intervals.
* Trade Mark Sample Parts by weight Parts by weight Suprasec DNR
Test 1 0.78 100 Test 2 0.96 100 Test 3 1.32 100 Test 4 1.67 100 Test 5 2.03 100 Test 6 2.38 100 Test 7 0.80 100 Test 8 1.00 100 Test 9 1.40 100 Test 10 1.80 100 Test 11 2.20 100 Test 12 2.60 100 As a comparison a number of compositions comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and various amounts of the samples designated 5 Comparison 1 to 6 (see Table 5 below) were made up. All these compositions contained the same amount of Product A, this amount being the same as the amount of Product A in each of the compositions designated Test 1 to Test 12.
These compositions were then stored at 450 C and the viscosity tested using a Brookfield viscometer at the same intervals.
Sample Parts by weight Parts by weight Suprasec DNR
Comparison 1 1.1 100 Comparison 2 1.6 100 Comparison 3 2.6 100 Comparison 4 3.6 100 Comparison 5 4.6 100 Comparison 6 5.6 100 The following results were obtained for the systems based on Product A
with various added amounts of methylacetoacetate and ethylacetoacetate [all results are reported in Pa s].
Product A + Methy/acetoacetate Time Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 (Days) 0 0.292 0.288 0.274 0.272 0.267 0.267 14 0.828 0.548 0.632 0.678 0.746 0.806 25 1.208 0.734 0.840 1.007 1.078 1.153 30 n.m. 1.050 1.139 1.330 1.526 1.756 46 2.568 1.207 1.239 1.546 1.767 2.125 67 n.m. 1.917 1.707 2.209 2.579 3.392 n.m. = not measured Product A + Ethylacetoacetate Time Test 7 Test 8 Test 9 Test 10 Test 11 Test 12 (Days) 0 0.305 0.293 0.280 0.270 0.263 0.263 14 0.787 0.600 0.645 0.717 0.806 0.814 25 1.136 0.879 0.911 1.078 1.197 1.251 30 n.m. 1.137 1.225 1.538 1.734 1.811 46 2.486 1.310 1.410 1.735 2.240 2.018 67 n.m. 2.028 1.943 2.440 3.275 3.192 n.m. = not measured The following results were obtained for the systems based on Product A
with various added amounts of cetylacetoacetate [all results reported in Pa s].
Product A + Cetylacetoacetate Time Comparison Comparison Comparison Comparison Comparison Comparison (Days) 1 2 3 4 5 6 0 0.324 0.296 0.296 0.277 0.279 0.264 14 1.195 0.599 0.627 0.630 0.667 0.626 25 1.995 0.797 0.839 0.851 1.014 0.989 30 n.m. 1.145 1.168 1.049 1.430 1.427 46 4.620 1.396 1.281 1.162 1.608 1.620 67 n.m. 2.443 1.853 1.610 2.260 2.309 n. m. = not measured Generally, the most relevant period for storage stability at room temperature is the period 14 to 46 days after production of a polyisocyanate composition. From Tables 6 to 8 above, it can be seen that the optimum (generally, lowest) viscosity after 46 days at 45 C (an accelerated test) is achieved in Test 2 (2.2 moles methylacetoacetate), Test 8 (2.2 moles ethylacetoacetate) and Comparison 4 (6.6 moles cetylacetoacetate). The results demonstrate that the titanium complexes used in the composition of the invention provide a more economical means of stabilising the polyisocyanate composition.
Preparation of Product B
A flask was charged with tetra-n-propyl zirconate (43.7g, Tilcom` NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a cold water bath. Methylacetoacetate (46.5g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a paie yellow liquid. The displaced alcohol (35.3g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (54.8g). The oil was then mixed with additional methylacetoacetate (11.6g) to yield PRODUCT B.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.09 parts by weight Product B was prepared in duplicate. The compositions were then stored at 450 C and the viscosity tested at various intervais using a Brookfield viscometer. Results are reported in Table 9 below in Pa s.
Time (Days) Product B(i) Product B(ii) 0 0.220 0.220 20 0.440 0.400 41 0.580 0.520 62 0.660 0.640 84 1.020 1.340 Preparation of Product C
A flask was charged with tetra-n-propyl zirconate (43.7g, Tilcom" NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a cold water bath. Methylacetoacetate (46.5g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (34.3g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (55.8g). The oil was then mixed with additional methylacetoacetate (23.2g) to yield PRODUCT C.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.48 parts by weight Product C was prepared in duplicate. The compositions were then stored at 45 C and the viscosity tested at various intervals using a Brookfield viscometer. Results are reported in Table 10 below in Pa s.
Time (Days) Product C(i) Product C(ii) 0 0.220 0.220 20 0.460 0.500 41 0.500 0.500 62 0.720 0.620 84 1.280 0.980 Preparation of Product D
A flask was charged with tetra-n-propyl zirconate (87.3g, Tilcom" NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a 5 cold water bath. Ethylacetoacetate (104g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid.
The displaced alcohol (67.1 g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (1 24.3g). The oil was then mixed with additional ethyl acetoacetate (26g) to yield PRODUCT D.
10 To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.21 parts by weight Product D was prepared in duplicate. The compositions were then stored at 45 C and the viscosity of the compositions tested at various intervals using a Brookfield viscometer.
Results 15 are reported in Table 11 below in Pa s.
Time (Days) Product D(i) Product D(ii) 0 0.220 0.220 20 0.480 0.460 41 0.540 0.560 62 0.700 0.920 84 1.140 1.040 Prenaration of Product E
A flask was charged with tetra-n-propyl zirconate (87.3g, Tilcom" NPZ
[75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (104g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid.
The displaced aicohol (70.0g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (121.4g). The oil was then mixed with additional ethylacetoacetate (52g) to yield PRODUCT E.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.56 parts by weight Product E was prepared in duplicate. The compositions were then stored at 450 C and the viscosity of the compositions tested at various intervals using a Brookfield viscometer.
Results are reported in Table 12 below in Pa s.
Time (Days) Product E(i) Product E(ii) 0 0.220 0.220 20 0.560 0.580 41 0.620 0.600 62 0.860 0.780 84 1.060 0.960 The zirconium complexes (Products B, C, D E) show improved stability over a longer period of time than the titanium complexes of Comparison 1 to 6 (Table 8).
Prenaration of Product F
A flask was charged with tetraisopropyl titanate (71 g, Tilcom` TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, distilled water (1.1g, 0.25 moles per mole Ti) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (43.4g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (94.5g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT F.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 0.88 parts by weight Product F was prepared. The composition was then stored at 45 C and the viscosity of the composition tested at various intervais using a Brookfield viscometer.
Preoaration of Product G
A flask was charged with tetraisopropyl titanate (71 g, TilcomA TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, distilled water (2.3g, 0.5 moles per mole of Ti) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (48.4g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (93.3g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT G.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 0.88 parts by weight Product G was prepared. The composition was then stored at 45 C and the viscosity of the composition tested at various intervals using a Brookfield viscometer. Results are reported for Product F and Product G in Table 13 below in Pa s.
Time (Days) Product F Product G
0 0.220 0.220 10 0.485 0.520 40 0.760 0.760 60 1.100 1.200 80 1.140 1.220 A flask was charged with tetraisopropyl titanate (71g, Tilcom' TIPT from ICI Vertec) and placed in a cold water bath. tert-Butylacetoacetate (79.1 g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (30.0g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (120.0g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT H.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 1.02 parts by weight Product H was prepared. The composition was then stored at 450 C and the viscosity of the composition tested at various intervals using a Brookfield viscometer. Results are reported in Table 14 below in Pa s.
Time (Days) Viscosity 0 ` 0.220 10 0.480 40 1.160 60 1.800 80 2.160 Preoaration of Product I
A flask was charged with tetraisopropyl titanate (71g, Tilcoma TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added 5 over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, butyl acid phosphate (11.4g, 0.25 moles) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (38.2g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (109.2g). This liquid was then mixed with additional ethyl 10 acetoacetate (65g) to yield PRODUCT I.
To evaiuate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical lndustries) and 0.97 parts by weight Product I was prepared in duplicate. The compositions were then stored at 45 C and the viscosity of the 15 compositions tested at various intervals using a Brookfield viscometer (see Table 15).
Preparation of Product J
A flask was charged with tetraisopropyl titanate (71 g, Tilcom` TIPT from ICI Vertec) and placed in a cold water bath. Ethyiacetoacetate (65g) was added 20 over a period of one hour whilst the mixture was stirred. Following addition of ethylacetoacetate, butyl acid phosphate (22.8g, 0.5 moles) was added to the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (40.8g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (118.0g). This liquid was then mixed with additional ethyl 25 acetoacetate (65g) to yield PRODUCT J.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 1.02 parts by weight Product J was prepared. The composition was then stored at 45 C and the viscosity of the composition tested at various intervals using a Brookfield viscometer. Results are reported for Product I and Product J in Table 15 below in Pa s.
Time (Days) Product I Product J
0 0.220 0.220 0.440 0.389 40 0.880 0.580 60 1.320 0.960 80 1.360 1.040
Claims (11)
1. An organometallic composition comprising a complex of at least one metal selected from the group consisting of titanium, zirconium and hafnium and an acetoacetate ester in which the molar ration of Ti or Hf to acetoacetate ester is in the range of 1:2.5 to 1:10 or the molar ratio of Zr to acetoacetate ester is in the range of 1:4.5 to 1:10 and said acetoacetate ester is an ester of an alcohol containing 1 to 6 carbon atoms.
2. An organometallic composition according to Claim 1 in which the complex is a complex of titanium having a molar ratio of Ti to acetoacetate ester in the range of 1:25 to 1:8.
3. An organometallic composition according to Claim 2 in which the molar ratio of Ti to acetoacetate ester is in the range 1:3 to 1:6.
4. An organometallic composition according to Claim 1 in which the complex is a complex of hafnium having a molar ratio of Hf to acetoacetate ester in the range 1:4.5 to 1:10.
5. An organometallic composition according to Claim 1 in which the molar ratio of Zr or Hf to acetoacetate ester is in the range 1:4.5 to 1:8.
6. An organometallic composition according to any one of claims 1 to 5 in which the acetoacetate ester is ethyl acetoacetate.
7. An organometallic composition according to any one of claims 1 to 6 in which the complex has been prepared by mixing a titanium, zirconium or hafnium alkoxide having the general formula M(OR)4 in which M is Ti, Zr or Hf and R is a substituted or unsubstituted, cyclic or linear, alkyl, alkenyl, aryl or alkyl-aryl group with said acetoacetate ester.
8. An organometallic composition according to Claim 7 in which R contains up to 6 carbon atoms.
9. An organometallic composition according to any one of claims 1 to 6 in which the complex has been prepared by mixing a condensed titanium, zirconium or hafnium alkoxide having the general formula RO[M(OR)2O]x R in which M is Ti, Zr or Hf, x is an integer from 2 to 16, and R is a substituted or unsubstituted, cyclic or linear, alkyl, alkenyl, aryl or alkyl-aryl group with said acetoacetate ester.
10. An organometallic composition according to Claim 9 in which the average value of x is in the range 2 to 8.
11. An organometallic composition according to any one of claims 7 to 10 in which displaced alcohol is removed after said mixing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9815029.5 | 1998-07-11 | ||
| GBGB9815029.5A GB9815029D0 (en) | 1998-07-11 | 1998-07-11 | Polyisocyanate compositions |
| PCT/GB1999/001982 WO2000002885A1 (en) | 1998-07-11 | 1999-06-24 | Organometallic compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2335481A1 CA2335481A1 (en) | 2000-01-20 |
| CA2335481C true CA2335481C (en) | 2009-09-15 |
Family
ID=10835324
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002335481A Expired - Fee Related CA2335481C (en) | 1998-07-11 | 1999-06-24 | Organometallic compositions |
| CA002344505A Expired - Lifetime CA2344505C (en) | 1998-07-11 | 1999-07-09 | Polyisocyanate compositions |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
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| CA002344505A Expired - Lifetime CA2344505C (en) | 1998-07-11 | 1999-07-09 | Polyisocyanate compositions |
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| Country | Link |
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| US (1) | US6288255B1 (en) |
| EP (2) | EP1097157B1 (en) |
| JP (1) | JP2002520434A (en) |
| CN (2) | CN1181078C (en) |
| AR (1) | AR019751A1 (en) |
| AT (2) | ATE224902T1 (en) |
| AU (2) | AU4383999A (en) |
| BR (2) | BR9912037B1 (en) |
| CA (2) | CA2335481C (en) |
| CO (1) | CO5100969A1 (en) |
| DE (2) | DE69903170T2 (en) |
| GB (1) | GB9815029D0 (en) |
| HK (1) | HK1039955A1 (en) |
| NO (1) | NO20010165L (en) |
| PL (2) | PL196091B1 (en) |
| RU (1) | RU2223276C2 (en) |
| WO (2) | WO2000002885A1 (en) |
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| GB0000569D0 (en) * | 2000-01-12 | 2000-03-01 | Ici Plc | Organometallic compositions |
| US7614507B2 (en) * | 2001-08-23 | 2009-11-10 | Pur Water Purification Products Inc. | Water filter materials, water filters and kits containing particles coated with cationic polymer and processes for using the same |
| US6838404B2 (en) * | 2002-01-09 | 2005-01-04 | Board Of Trustees Of University Of Illinois | Metal alkoxides and methods of making same |
| US7399438B2 (en) * | 2003-02-24 | 2008-07-15 | Jeld-Wen, Inc. | Thin-layer lignocellulose composites having increased resistance to moisture and methods of making the same |
| US6794315B1 (en) * | 2003-03-06 | 2004-09-21 | Board Of Trustees Of The University Of Illinois | Ultrathin oxide films on semiconductors |
| US7943070B1 (en) | 2003-05-05 | 2011-05-17 | Jeld-Wen, Inc. | Molded thin-layer lignocellulose composites having reduced thickness and methods of making same |
| CN1712482B (en) * | 2004-06-21 | 2010-05-05 | 日本聚氨酯工业株式会社 | Binding composition and production of plant fiber plates |
| CN101687348B (en) * | 2007-05-23 | 2014-11-12 | 亨斯迈国际有限责任公司 | Adhesives and processes for production of lignocellulosic composites using adhesives |
| EP2324071B2 (en) * | 2008-09-10 | 2022-05-04 | Dow Global Technologies LLC | Improved process for bonding reactive adhesives to substrates |
| US8058193B2 (en) | 2008-12-11 | 2011-11-15 | Jeld-Wen, Inc. | Thin-layer lignocellulose composites and methods of making the same |
| US8691005B2 (en) | 2011-07-20 | 2014-04-08 | Huntsman International Llc | Binder composition for use in cellulosic composites and methods related thereto |
| EP2794708A4 (en) | 2011-12-20 | 2015-08-26 | Huntsman Int Llc | A method of adjusting the tack value of a binder composition |
| BR112020003544A2 (en) | 2017-09-29 | 2020-08-25 | Huntsman International Llc | lignocellulosic mixture |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB890280A (en) * | 1959-02-25 | 1962-02-28 | Ici Ltd | Improvements in or relating to the manufacture of foamed polyurethanes |
| GB1444933A (en) | 1973-04-03 | 1976-08-04 | Ici Ltd | Emulsions of organic isocyanates |
| JPS6035334B2 (en) | 1977-03-09 | 1985-08-14 | 一郎 木島 | Method for producing metal chelate compounds |
| JPS5790014A (en) | 1980-11-25 | 1982-06-04 | Toshiba Corp | Epoxy resin composition |
| GB2147592A (en) * | 1983-10-06 | 1985-05-15 | Basf Wyandotte Corp | Reducing the viscosity of filled liquid polymers |
| EP0155036B1 (en) * | 1984-02-28 | 1987-11-19 | Shell Internationale Researchmaatschappij B.V. | Heat-curable polyepoxide-(meth)acrylate ester-styrene composition |
| JPS6169824A (en) * | 1984-08-02 | 1986-04-10 | Mitsui Toatsu Chem Inc | Polyurethane prepolymer of excellent storage stability |
| GB2212164B (en) | 1987-11-12 | 1992-01-29 | Kansai Paint Co Ltd | Low temperature curable composition |
| JP2948638B2 (en) | 1990-08-23 | 1999-09-13 | 関西ペイント株式会社 | Curable resin composition |
| GB9111559D0 (en) | 1991-05-29 | 1991-07-17 | Ici Plc | Polyisocyanate composition |
| GB9116267D0 (en) | 1991-07-27 | 1991-09-11 | Tioxide Chemicals Limited | Aqueous compositions |
| JP3282882B2 (en) | 1993-05-07 | 2002-05-20 | ナミックス株式会社 | Dielectric protective agent |
| DE69503939T2 (en) | 1994-03-02 | 1999-01-21 | Konishiroku Photo Ind | Electrophotographic photoconductor |
| GB9412579D0 (en) * | 1994-06-22 | 1994-08-10 | Tioxide Specialties Ltd | Compositions containing zirconium compounds |
| FR2727675A1 (en) | 1994-12-01 | 1996-06-07 | Carlucci Pierre Antoine | Compsns. for making insulating materials |
| JPH0922134A (en) | 1995-07-04 | 1997-01-21 | Konica Corp | Electrophotographic photoreceptor and image forming method |
| JP3692567B2 (en) | 1995-09-14 | 2005-09-07 | コニカミノルタホールディングス株式会社 | Electrophotographic photoreceptor and image forming apparatus and method |
| AU7298096A (en) * | 1995-11-06 | 1997-05-29 | Huntsman Ici Chemicals Llc | Polyisocyanate composition |
| JPH09286007A (en) * | 1996-02-22 | 1997-11-04 | Nippon Polyurethane Ind Co Ltd | Manufacture of lignocellulose material molding body |
| FR2747675B1 (en) | 1996-04-19 | 1998-05-22 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF (METH) ACRYLATES |
| BR9711862A (en) * | 1996-10-05 | 2001-08-28 | Tioxide Specialties Ltd | Catalyst, and, curing process of a composition |
-
1998
- 1998-07-11 GB GBGB9815029.5A patent/GB9815029D0/en not_active Ceased
-
1999
- 1999-06-24 AU AU43839/99A patent/AU4383999A/en not_active Abandoned
- 1999-06-24 AT AT99926663T patent/ATE224902T1/en not_active IP Right Cessation
- 1999-06-24 DE DE69903170T patent/DE69903170T2/en not_active Expired - Lifetime
- 1999-06-24 CN CNB99808526XA patent/CN1181078C/en not_active Expired - Fee Related
- 1999-06-24 PL PL345450A patent/PL196091B1/en unknown
- 1999-06-24 WO PCT/GB1999/001982 patent/WO2000002885A1/en active IP Right Grant
- 1999-06-24 RU RU2001103754/04A patent/RU2223276C2/en not_active IP Right Cessation
- 1999-06-24 BR BRPI9912037-2A patent/BR9912037B1/en not_active IP Right Cessation
- 1999-06-24 CA CA002335481A patent/CA2335481C/en not_active Expired - Fee Related
- 1999-06-24 EP EP99926663A patent/EP1097157B1/en not_active Expired - Lifetime
- 1999-07-08 AR ARP990103332A patent/AR019751A1/en unknown
- 1999-07-09 CA CA002344505A patent/CA2344505C/en not_active Expired - Lifetime
- 1999-07-09 EP EP99934648A patent/EP1098921B1/en not_active Expired - Lifetime
- 1999-07-09 CN CN99808530A patent/CN1309677A/en active Pending
- 1999-07-09 DE DE69925490T patent/DE69925490T2/en not_active Expired - Lifetime
- 1999-07-09 JP JP2000559170A patent/JP2002520434A/en not_active Withdrawn
- 1999-07-09 BR BR9911958-7A patent/BR9911958A/en not_active Application Discontinuation
- 1999-07-09 WO PCT/EP1999/004844 patent/WO2000002941A1/en active IP Right Grant
- 1999-07-09 CO CO99043313A patent/CO5100969A1/en unknown
- 1999-07-09 AT AT99934648T patent/ATE296323T1/en not_active IP Right Cessation
- 1999-07-09 PL PL345420A patent/PL200642B1/en unknown
- 1999-07-09 AU AU50350/99A patent/AU5035099A/en not_active Abandoned
- 1999-12-08 US US09/456,583 patent/US6288255B1/en not_active Expired - Lifetime
-
2001
- 2001-01-10 NO NO20010165A patent/NO20010165L/en not_active Application Discontinuation
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2002
- 2002-02-18 HK HK02101169.1A patent/HK1039955A1/en unknown
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